CN108165052A - A kind of ceramic pigment with near-infrared reflection and preparation method thereof - Google Patents
A kind of ceramic pigment with near-infrared reflection and preparation method thereof Download PDFInfo
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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Abstract
The invention discloses a kind of ceramic pigments with near-infrared reflection and preparation method thereof.The ceramic pigment microstructure of the present invention includes the titanium dioxide shell structurre of spherical titanium dioxide core and chromium, vanadium and antimony codope, and the grain size of the spherical titanium dioxide core is adjustable in the range of 100~2000nm, the thickness of the titanium dioxide shell of the chromium, vanadium and antimony codope is adjustable in the range of 20~500nm.After the preparation method by titanium source by hydrolyzing balling-up, coloring ion absorption is carried out, is finally heat-treated by high temperature, obtain described there is the ceramic pigment of near-infrared reflection.The ceramic pigment of the present invention has many advantages, such as that near infrared reflectivity is high, monodispersity is good, microscopic appearance is controllable for spherical and colorant granularity.
Description
Technical field
The present invention relates to ceramic pigment preparing technical field more particularly to a kind of there is the ceramic pigment of near-infrared reflection
Material and preparation method thereof.
Background technology
With the continuous development of urban construction, urban environment load increasingly sharpens.Simply because urban green space is reduced and the sun
The tropical island effect that intense radiation is formed, makes down town temperature be higher by about 3~5 DEG C than surrounding area.These heats are in building
Surface is accumulated, and while increasing own temperature, can also be transferred heat to interior of building, be led to indoor temperature liter
Height, and then the comfort level of reduced circumstances, increase air conditioner refrigerating electricity consumption.Using skin heat preservation technology to the north
It is highly effective that area, which reduces heating energy consumption, and the effect that air conditioner refrigerating energy consumption is reduced to southern area is not obvious.It is flourishing
Country is one of common method of building energy conservation using highly reflective material in external wall.Under normal conditions, outside building
A small amount of solar radiation can be only reflected, most solar radiation is all absorbed by building roof or exterior wall.Reflective materials have
There is heat insulation, material itself near-infrared reflection function is mainly utilized and reflects away most sunlight, reduce building
The temperature on object surface so as to promote indoor comfort degree, effectively reduces building air-conditioning energy consumption.
Titan yellow tone is the common decoration style of skin.At present, titan yellow colorant is mainly with rutile titanium dioxide
Titanium is basis material, using metals such as chromium, nickel as color development element.Rutile TiO2It is most early in the extensive use of heat insulating coat field
One of inorganic pigment.Find that its light reflectivity near infrared band is up to more than 85% by spectrum test.Chinese invention
Patent CN106675112A discloses a kind of high coloring power pigment-level titan yellow color production method, selects nanoscale hydrated titanium dioxide
For raw material, addition titanic acid-sol, Zn-ef ficiency, antimony oxide, aluminium salt, phosphoric acid, nickel oxide are made through high-temperature calcination, crushing, desalination
Product.Chinese invention patent CN103613958A discloses environmentally-friendly titanium type pigment prepared by a kind of complexing-depositing technology, with titanium white
Powder, antimony oxide are raw material, and solution is formed, then pass through solution acid alkalinity tune by the stable dispersion of coloring ion and complexing agent
Section, makes coloring ion homogeneous precipitation in titanium dioxide and antimony oxide raw material, and titanium is obtained by the techniques such as being spray-dried, calcining
Yellow material.But titan yellow colorant broad particle distribution prepared by existing method, granule-morphology are irregular.The present invention provides a kind of tool
There is titan yellow colorant of near-infrared reflection function and preparation method thereof, titan yellow colorant prepared by this method has near infrared reflectivity
The advantages that height, monodispersity is good, and microscopic appearance is spherical, and colorant granularity is controllable.
Invention content
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to providing a kind of has the function of the ceramics of near-infrared reflection
Colorant, specially titan yellow colorant.
The present invention also aims to provide a kind of preparation side with the ceramic pigment of near-infrared reflection
Method.After the preparation method by titanium source by hydrolyzing balling-up, coloring ion absorption is carried out, is finally heat-treated, obtains by high temperature
It is described that there is the ceramic pigment of near-infrared reflection.
The purpose of the present invention is achieved through the following technical solutions.
A kind of to have the function of the ceramic pigment of near-infrared reflection, microstructure is spherical nucleocapsid, including spherical two
The titanium dioxide shell of titanium oxide core and chromium, vanadium and antimony codope；
The grain size of the spherical titanium dioxide core is adjustable in the range of 100~2000nm；The chromium, vanadium and antimony are co-doped with
The thickness of miscellaneous titanium dioxide shell is adjustable in the range of 20~500nm.
A kind of method with the ceramic pigment of near-infrared reflection described above is prepared, is included the following steps：
(1) butyl titanate is added in absolute alcohol, after stirring and evenly mixing, adds in deionized water, continue stirring until obtaining
White precipitate；White precipitate is collected by centrifugation, and is washed with absolute ethyl alcohol, obtains the spherical titanium dioxide granule of monodisperse；
(2) prepared chromium nitrate solution, ammonium tungstate solution and antimony chloride solution are added in glacial acetic acid solution, stirred
Mixing is mixed, obtains solution A；
(3) butyl titanate is added in absolute ethyl alcohol or anhydrous propyl alcohol, after stirring and evenly mixing, adds in citric acid, continue to stir
Mixing is mixed, adds polyvinylpyrrolidone, is further continued for stirring and evenly mixing, obtains solution B；
(4) solution A is added in solution B, stirs and evenly mixs to obtain mixed solution；Again by the spherical titanium dioxide granule of monodisperse
It adds in obtained mixed solution, continues that precipitation is collected by centrifugation after stirring and evenly mixing, the precipitation of collection is placed in electric furnace after drying
In be heat-treated, cool down, obtain described there is the ceramic pigment of near-infrared reflection.
Further, in step (1), the absolute alcohol is more than 3 polyalcohol for carbon atom number.
Further, in step (1), the amount ratio of the butyl titanate and absolute alcohol is 0.05~0.25: 300mol/
mL。
Further, in step (1), the time stirred and evenly mixed is 5~30min.
Further, in step (1), the dosage of the deionized water and the dosage volume ratio of absolute alcohol are 5~50: 300.
Further, in step (1), the time for continuing stirring is 5~20min.
Further, in step (1), the number of the absolute ethyl alcohol washing is 3~5 times.
Further, in step (2), a concentration of 0.01~0.03mol/L of the chromium nitrate solution.
Further, in step (2), a concentration of 0.005~0.015mol/L of the ammonium tungstate solution.
Further, in step (2), a concentration of 0.01~0.02mol/L of the antimony chloride solution.
Further, in step (2), a concentration of 0.05~0.15mol/L of the glacial acetic acid solution.
Further, in step (2), the chromium nitrate solution, ammonium tungstate solution, antimony chloride solution and glacial acetic acid solution
Volume ratio be 1: 0.5~1: 0.5~0.75: 0.5~0.75.
Further, in step (3), the amount ratio of the butyl titanate and absolute ethyl alcohol or anhydrous propyl alcohol for 0.05~
0.15∶200mol/mL。
Further, in step (3), the time stirred and evenly mixed is 5~10min.
Further, in step (3), the molar ratio of the butyl titanate and citric acid for 0.05~0.15: 0.05~
0.25。
Further, it is described to continue the time stirred and evenly mixed as 10~20min in step (3).
Further, in step (3), the mass ratio of the butyl titanate and polyvinylpyrrolidone is 17~51: 0.5
~1.5.
Further, in step (3), after adding in polyvinylpyrrolidone, be further continued for the time stirred and evenly mixed for 10~
30min。
Further, in step (4), the mixed volume ratio of the solution A and solution B is 0.5: 1~5.
Further, in step (4), solution A is 1~1.5 hour with the time that solution B stirs and evenly mixs.
Further, in step (4), the solid-liquid ratio of the spherical titanium dioxide granule of the monodisperse and mixed solution for 50~
100: 80~150g/mL.
Further, in step (4), after adding in the spherical titanium dioxide granule of monodisperse, the time for continuing to stir and evenly mix is
0.5~5 hour.
Further, in step (4), the drying is 1~1.5 hour dry at 80~100 DEG C.
Further, in step (4), the heat treatment be warming up to 700 with the heating rate of 250~300 DEG C/h~
After 1100 DEG C, heat preservation heat treatment 3~5 hours.
Further, in step (4), the cooling is to be cooled to room temperature.
Compared with prior art, the invention has the advantages that and advantageous effect：
(1) ceramic pigment of the invention is near infrared reflectivity is high, monodispersity is good, microscopic appearance is spherical and color
The advantages that material granularity is controllable；
(2) preparation method simple process and low cost of the invention, energy consumption is few, is advantageously implemented industrialization large-scale production.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph with the ceramic pigment of near-infrared reflection prepared by embodiment 1；
Fig. 2 has the function of the near infrared reflectivity curve graph of the ceramic pigment of near-infrared reflection for prepared by embodiment 1.
Specific embodiment
Technical solution of the present invention is described in further detail below in conjunction with specific embodiment and attached drawing, but the present invention
Embodiment and protection domain are without being limited thereto.
In specific examples below, the raw material referred to is unspecified, is commercial product；The processing step that refers to or
Preparation method is unspecified, is processing step known to a person skilled in the art or preparation method.
Embodiment 1
Preparing has the function of the ceramic pigment of near-infrared reflection, specifically includes following processing step：
(1) 0.05mol butyl titanates are added in 300mL anhydrous normal butyl alcohols, stir 5min after, add in 50mL go from
Sub- water continues to stir 5min, obtains the precipitation of white；
(2) white precipitate prepared in step (1) is collected by centrifugation, and is washed 5 times using absolute ethyl alcohol, obtain list
Disperse spherical titanium dioxide particle, the average grain diameter of particle is 300nm；
(3) compound concentration is the glacial acetic acid solution of 0.15mol/L, the chromic nitrate that another compound concentration respectively is 0.02mol/L
The antimony chloride solution of solution, the ammonium tungstate solution of 0.015mol/L and 0.01mol/L, will by 1: 0.5: 0.6: 0.5 volume ratio
Chromium nitrate solution, ammonium tungstate solution and antimony chloride solution are added in glacial acetic acid solution, are uniformly mixed, are obtained solution A；
(4) 0.1mol butyl titanates are added in 200mL absolute ethyl alcohols, after stirring 5min, add in the lemon of 0.1mol
Acid stirs 10min as chelating agent, then adds in the polyvinylpyrrolidone of 0.5g, after stirring 10min, obtains solution
B；
(5) solution A is added in solution B (mixed volume ratio 0.5: 1), is mixed 1 hour, obtains solution C；
(6) by the spherical titanium dioxide granule of the monodisperse of step (2) add in step (5) solution C (solid-liquid ratio 50:
In 150g/mL), stirring carries out centrifugal treating after 0.5 hour, and centrifugation product is placed in 100 DEG C of baking ovens, 1 hour dry,
Then dry product is placed in electric furnace, is warming up to 850 DEG C with 300 DEG C/h of heating rates, heat preservation heat treatment 3 hours is cold
But to room temperature, obtain described there is the ceramic pigment of near-infrared reflection.
The scanning electron microscope (SEM) photograph of the ceramic pigment of preparation is as shown in Figure 1, as shown in Figure 1, the ceramic pigment monodispersity of preparation
Good, microscopic appearance is spherical, average grain diameter 350nm；Ceramic pigment integrally includes spherical titanium dioxide core and chromium, vanadium
With the titanium dioxide shell of antimony codope.
The near infrared reflectivity curve graph of the ceramic pigment of preparation is as shown in Fig. 2, as shown in Figure 2, the ceramic pigment of preparation
Near infrared reflectivity be about 80%, and the near infrared reflectivity of common colorant is about 70%.
Embodiment 2
Preparing has the function of the ceramic pigment of near-infrared reflection, specifically includes following processing step：
(1) 0.15mol butyl titanates are added to 300mL without in n-butanol, after stirring 5min, add in the deionization of 5mL
Water continues to stir 5min, obtains the precipitation of white；
(2) white precipitate prepared in step (1) is collected by centrifugation, and is washed 5 times using absolute ethyl alcohol, obtain list
Disperse spherical titanium dioxide particle, the average grain diameter of particle is 450nm；
(3) compound concentration is the glacial acetic acid solution of 0.05mo1/L, the chromic nitrate that another compound concentration respectively is 0.015mol/L
The antimony chloride solution of solution, the ammonium tungstate solution of 0.01mol/L and 0.02mol/L, will by 1: 0.5: 0.75: 0.75 volume ratio
Chromium nitrate solution, ammonium tungstate solution and antimony chloride solution are added in glacial acetic acid solution, are uniformly mixed, are obtained solution A；
(4) 0.1mol butyl titanates are added in 200mL absolute ethyl alcohols, after stirring 5min, add in the lemon of 0.1mol
Acid stirs 10min as chelating agent, then adds in the polyvinylpyrrolidone of 0.5g, after stirring 10min, obtains solution
B；
(5) solution A is added in solution B (mixed volume ratio 0.5: 2), is mixed 1 hour, obtains solution C；
(6) the spherical titanium dioxide granule of the monodisperse of step (2) is added in into step (5) solution C (solid-liquid ratio 70: 120g/
ML in), stirring carries out centrifugal treating after 0.5 hour, and centrifugation product is placed in 100 DEG C of baking ovens, 1 hour dry, then
Dry product is placed in electric furnace, is warming up to 700 DEG C with 300 DEG C/h of heating rates, heat preservation heat treatment 3 hours is cooled to
Room temperature obtains described having the function of the ceramic pigment of near-infrared reflection.
The ceramic pigment monodispersity of preparation is good, and microscopic appearance is spherical, and ceramic pigment integrally includes spherical titanium dioxide
The titanium dioxide shell of titanium core and chromium, vanadium and antimony codope, the average grain diameter of ceramic pigment are 630nm, near-infrared reflection
Rate 78%.
Embodiment 3
Preparing has the function of the ceramic pigment of near-infrared reflection, specifically includes following processing step：
(1) 0.05mol butyl titanates are added in the anhydrous butanol of 300mL, after stirring 5min, add in the deionization of 25mL
Water continues to stir 5min, obtains the precipitation of white；
(2) white precipitate prepared in step (1) is collected by centrifugation, and is washed 5 times using absolute ethyl alcohol, obtain list
Disperse spherical titanium dioxide particle, the average grain diameter of particle is 800nm；
(3) compound concentration is the glacial acetic acid solution of 0.15mol/L, the chromic nitrate that another compound concentration respectively is 0.02mol/L
The antimony chloride solution of solution, the ammonium tungstate solution of 0.01mol/L and 0.01mol/L, will by 1: 0.75: 0.6: 0.6 volume ratio
Chromium nitrate solution, ammonium tungstate solution and antimony chloride solution are added in glacial acetic acid solution, are uniformly mixed, are obtained solution A；
(4) 0.15mol butyl titanates are added to 200mL without in ethyl alcohol, after stirring 5min, add in the citric acid of 0.1mol
As chelating agent, and 10min is stirred, then add in the polyvinylpyrrolidone of 1g, after stirring 10min, obtain solution B；
(5) solution A is added in solution B (mixed volume ratio 0.5: 3), is mixed 1 hour, obtains solution C；
(6) by the spherical titanium dioxide granule of the monodisperse of step (2) add in step (5) solution C (solid-liquid ratio 100:
In 150g/mL), stirring carries out centrifugal treating after 2 hours, and centrifugation product is placed in 100 DEG C of baking ovens, 1 hour dry, with
Dry sample is placed in electric furnace afterwards, is warming up to 1000 DEG C with 300 DEG C/h of heating rates, heat preservation heat treatment 3 hours is cold
But to room temperature, obtain described there is the ceramic pigment of near-infrared reflection.
The ceramic pigment monodispersity of preparation is good, and microscopic appearance is spherical, and ceramic pigment integrally includes spherical titanium dioxide
The titanium dioxide shell of titanium core and chromium, vanadium and antimony codope, the average grain diameter of ceramic pigment are 1200nm, near-infrared reflection
Rate 75%.
Embodiment 4
Preparing has the function of the ceramic pigment of near-infrared reflection, specifically includes following processing step：
(1) 0.15mol butyl titanates are added in the anhydrous amylalcohols of 300mL, after stirring 5min, add in the deionization of 20mL
Water continues to stir 5min, obtains the precipitation of white；
(2) white precipitate prepared in step (1) is collected by centrifugation, and is washed 5 times using absolute ethyl alcohol, obtain list
Disperse spherical titanium dioxide particle, the average grain diameter of particle is 1500nm；
(3) compound concentration is the glacial acetic acid solution of 0.1mol/L, and another compound concentration respectively is that the chromic nitrate of 0.01mol/L is molten
The antimony chloride solution of liquid, the ammonium tungstate solution of 0.005mol/L and 0.02mol/L, by 1: 1: 0.75: 0.6 volume ratio by nitric acid
Chromium solution, ammonium tungstate solution and antimony chloride solution are added in glacial acetic acid solution, are uniformly mixed, are obtained solution A；
(4) 0.15mol butyl titanates are added in 200mL anhydrous propyl alcohols, after stirring 5min, add in the lemon of 0.25mol
Lemon acid stirs 10min as chelating agent, then adds in the polyvinylpyrrolidone of 1.5g, after stirring 10min, obtains molten
Liquid B；
(5) solution A is added in solution B (mixed volume ratio 0.5: 1), is mixed 1 hour, obtains solution C；
(6) by the spherical titanium dioxide granule of the monodisperse of step (2) add in step (5) solution C (solid-liquid ratio 100:
In 120g/mL), stirring carries out centrifugal treating after 4 hours, and centrifugation product is placed in 100 DEG C of baking ovens, 1 hour dry, with
Dry product is placed in electric furnace afterwards, is warming up to 1100 DEG C with 300 DEG C/h of heating rates, heat preservation heat treatment 3 hours is cold
But to room temperature, obtain described there is the ceramic pigment of near-infrared reflection.
The ceramic pigment monodispersity of preparation is good, and microscopic appearance is spherical, and ceramic pigment integrally includes spherical titanium dioxide
The titanium dioxide shell of titanium core and chromium, vanadium and antimony codope, the average grain diameter of ceramic pigment are 2000nm, near-infrared reflection
Rate 81%.
Embodiment 5
Preparing has the function of the ceramic pigment of near-infrared reflection, specifically includes following processing step：
(1) 0.05mol butyl titanates are added in 300mL anhydrous normal butyl alcohols, after stirring 30min, add in going for 50mL
Ionized water continues to stir 20min, obtains the precipitation of white；
(2) white precipitate prepared in step (1) is collected by centrifugation, and is washed 3 times using absolute ethyl alcohol, obtain list
Disperse spherical titanium dioxide particle, the average grain diameter of particle is 100nm；
(3) compound concentration is the glacial acetic acid solution of 0.15mol/L, the chromic nitrate that another compound concentration respectively is 0.02mol/L
The antimony chloride solution of solution, the ammonium tungstate solution of 0.015mol/L and 0.01mol/L, will by 1: 0.5: 0.6: 0.7 volume ratio
Chromium nitrate solution, ammonium tungstate solution and antimony chloride solution are added in glacial acetic acid solution, are uniformly mixed, are obtained solution A；
(4) 0.1mol butyl titanates are added in 200mL absolute ethyl alcohols, after stirring 5min, add in the lemon of 0.1mol
Acid stirs 10min as chelating agent, then adds in the polyvinylpyrrolidone of 0.5g, after stirring 30min, obtains solution
B；
(5) solution A is added in solution B (mixed volume ratio 0.5: 5), is mixed 1.2 hours, obtains solution C；
(6) by the spherical titanium dioxide granule of the monodisperse of step (2) add in step (5) solution C (solid-liquid ratio 50:
In 150g/mL), stirring carries out centrifugal treating after 0.5 hour, and centrifugation product is placed in 100 DEG C of baking ovens, and dry 1.3 is small
When, then dry product is placed in electric furnace, is warming up to 850 DEG C with 280 DEG C/h of heating rates, heat preservation heat treatment 4 is small
When, it is cooled to room temperature, obtains described there is the ceramic pigment of near-infrared reflection.
The ceramic pigment monodispersity of preparation is good, and microscopic appearance is spherical, and ceramic pigment integrally includes spherical titanium dioxide
The titanium dioxide shell of titanium core and chromium, vanadium and antimony codope, the average grain diameter of ceramic pigment are 120nm, near-infrared reflection
Rate 85%.
Embodiment 6
Preparing has the function of the ceramic pigment of near-infrared reflection, specifically includes following processing step：
(1) 0.15mol butyl titanates are added to 300mL without in n-butanol, after stirring 5min, add in the deionization of 5mL
Water continues to stir 5min, obtains the precipitation of white；
(2) white precipitate prepared in step (1) is collected by centrifugation, and is washed 4 times using absolute ethyl alcohol, obtain list
Disperse spherical titanium dioxide particle, the average grain diameter of particle is 600nm；
(3) compound concentration is the glacial acetic acid solution of 0.05mol/L, the chromic nitrate that another compound concentration respectively is 0.015mol/L
The antimony chloride solution of solution, the ammonium tungstate solution of 0.01mol/L and 0.02mol/L, will by 1: 0.5: 0.75: 0.5 volume ratio
Chromium nitrate solution, ammonium tungstate solution and antimony chloride solution are added in glacial acetic acid solution, are uniformly mixed, are obtained solution A；
(4) it will O.1mol butyl titanate be added in 200mL absolute ethyl alcohols, and after stirring 5min, add in the lemon of 0.1mol
Acid stirs 10min as chelating agent, then adds in the polyvinylpyrrolidone of 0.5g, after stirring 10min, obtains solution
B；
(5) solution A is added in solution B (mixed volume ratio 0.5: 2), is mixed 1 hour, obtains solution C；
(6) the spherical titanium dioxide granule of the monodisperse of step (2) is added in into step (5) solution C (solid-liquid ratio 70: 120g/
ML in), stirring carries out centrifugal treating after 0.5 hour, and centrifugation product is placed in 100 DEG C of baking ovens, 1 hour dry, then
Dry product is placed in electric furnace, is warming up to 700 DEG C with 300 DEG C/h of heating rates, heat preservation heat treatment 3 hours is cooled to
Room temperature obtains described having the function of the ceramic pigment of near-infrared reflection.
The ceramic pigment monodispersity of preparation is good, and microscopic appearance is spherical, and ceramic pigment integrally includes spherical titanium dioxide
The titanium dioxide shell of titanium core and chromium, vanadium and antimony codope, the average grain diameter of ceramic pigment are 780nm, near-infrared reflection
Rate 79%.
Embodiment 7
Preparing has the function of the ceramic pigment of near-infrared reflection, specifically includes following processing step：
(1) 0.05mol butyl titanates are added in the anhydrous butanol of 300mL, stir 10min after, add in 25mL go from
Sub- water continues to stir 20min, obtains the precipitation of white；
(2) white precipitate prepared in step (1) is collected by centrifugation, and is washed 4 times using absolute ethyl alcohol, obtain list
Disperse spherical titanium dioxide particle, the average grain diameter of particle is 1050nm；
(3) compound concentration is the glacial acetic acid solution of 0.15mol/L, the chromic nitrate that another compound concentration respectively is 0.02mol/L
The antimony chloride solution of solution, the ammonium tungstate solution of 0.01mol/L and 0.01mol/L, will by 1: 0.75: 0.6: 0.75 volume ratio
Chromium nitrate solution, ammonium tungstate solution and antimony chloride solution are added in glacial acetic acid solution, are uniformly mixed, are obtained solution A；
(4) 0.15mol butyl titanates are added to 200mL without in ethyl alcohol, after stirring 5min, add in the citric acid of 0.1mol
As chelating agent, and 10min is stirred, then add in the polyvinylpyrrolidone of 1g, after stirring 15min, obtain solution B；
(5) solution A is added in solution B (mixed volume ratio 0.5: 3), is mixed 1.2 hours, obtains solution C；
(6) by the spherical titanium dioxide granule of the monodisperse of step (2) add in step (5) solution C (solid-liquid ratio 100:
In 150g/mL), stirring carries out centrifugal treating after 2 hours, and centrifugation product is placed in 90 DEG C of baking ovens, 1 hour dry, with
Dry sample is placed in electric furnace afterwards, is warming up to 1000 DEG C with 300 DEG C/h of heating rates, heat preservation heat treatment 4 hours is cold
But to room temperature, obtain described there is the ceramic pigment of near-infrared reflection.
The ceramic pigment monodispersity of preparation is good, and microscopic appearance is spherical, and ceramic pigment integrally includes spherical titanium dioxide
The titanium dioxide shell of titanium core and chromium, vanadium and antimony codope, the average grain diameter of ceramic pigment are 1530nm, near-infrared reflection
Rate 82%.
Embodiment 8
Preparing has the function of the ceramic pigment of near-infrared reflection, specifically includes following processing step：
(1) 0.15mol butyl titanates are added in the anhydrous amylalcohols of 300mL, after stirring 5min, add in the deionization of 20mL
Water continues to stir 5min, obtains the precipitation of white；
(2) white precipitate prepared in step (1) is collected by centrifugation, and is washed 5 times using absolute ethyl alcohol, obtain list
Disperse spherical titanium dioxide particle, the average grain diameter of particle is 2000nm；
(3) compound concentration is the glacial acetic acid solution of 0.1mol/L, and another compound concentration respectively is that the chromic nitrate of 0.01mol/L is molten
The antimony chloride solution of liquid, the ammonium tungstate solution of 0.005mol/L and 0.02mol/L, by 1: 1: 0.75: 0.7 volume ratio by nitric acid
Chromium solution, ammonium tungstate solution and antimony chloride solution are added in glacial acetic acid solution, are uniformly mixed, are obtained solution A；
(4) 0.15mol butyl titanates are added in 200mL anhydrous propyl alcohols, after stirring 5min, add in the lemon of 0.25mol
Lemon acid stirs 10min as chelating agent, then adds in the polyvinylpyrrolidone of 1.5g, after stirring 10min, obtains molten
Liquid B；
(5) solution A is added in solution B (mixed volume ratio 0.5: 4), is mixed 1 hour, obtains solution C；
(6) by the spherical titanium dioxide granule of the monodisperse of step (2) add in step (5) solution C (solid-liquid ratio 100:
In 120g/mL), stirring carries out centrifugal treating after 3 hours, and centrifugation product is placed in 100 DEG C of baking ovens, 1 hour dry, with
Dry product is placed in electric furnace afterwards, 1100 DEG C are warming up to 300 DEG C/h of heating rates, heat preservation is heat-treated 3.5 hours,
It is cooled to room temperature, obtains described there is the ceramic pigment of near-infrared reflection.
The ceramic pigment monodispersity of preparation is good, and microscopic appearance is spherical, and ceramic pigment integrally includes spherical titanium dioxide
The titanium dioxide shell of titanium core and chromium, vanadium and antimony codope, the average grain diameter of ceramic pigment are 2500nm, near-infrared reflection
Rate 84%.
Above example is only preferrred embodiment of the present invention, is only used for explaining the present invention, be not intended to limit the present invention, this
Any change that field technology personnel are made under without departing from spirit of the invention and principle, replacement, combine, simplification, modification
Deng should be equivalent substitute mode, should be included within the scope of the present invention.
Claims (10)
1. a kind of have the function of the ceramic pigment of near-infrared reflection, which is characterized in that microstructure is spherical nucleocapsid, including
The titanium dioxide shell of spherical titanium dioxide core and chromium, vanadium and antimony codope；The spherical titanium dioxide core
Grain size is adjustable in the range of 100~2000nm；The thickness of the titanium dioxide shell of the chromium, vanadium and antimony codope 20~
It is adjustable in the range of 500nm.
2. prepare a kind of method with the ceramic pigment of near-infrared reflection described in claim 1, which is characterized in that packet
Include following steps：
(1) butyl titanate is added in absolute alcohol, after stirring and evenly mixing, adds in deionized water, continue stirring until obtaining white
Precipitation；White precipitate is collected by centrifugation, and is washed with absolute ethyl alcohol, obtains the spherical titanium dioxide granule of monodisperse；
(2) prepared chromium nitrate solution, ammonium tungstate solution and antimony chloride solution are added in glacial acetic acid solution, stirring is mixed
It is even, obtain solution A；
(3) butyl titanate is added in absolute ethyl alcohol or anhydrous propyl alcohol, after stirring and evenly mixing, adds in citric acid, it is mixed to continue stirring
It is even, polyvinylpyrrolidone is added, is further continued for stirring and evenly mixing, obtains solution B；
(4) solution A is added in solution B, stirs and evenly mixs to obtain mixed solution；The spherical titanium dioxide granule of monodisperse is added in again
In obtained mixed solution, continue that precipitation is collected by centrifugation after stirring and evenly mixing, by the precipitation of collection be placed in after drying in electric furnace into
Row heat treatment, cooling obtain described having the function of the ceramic pigment of near-infrared reflection.
3. preparation method according to claim 2, which is characterized in that in step (1), the absolute alcohol is big for carbon atom number
In 3 polyalcohol；The amount ratio of the butyl titanate and absolute alcohol is 0.05~0.25: 300mol/mL；It is described to stir and evenly mix
Time is 5~30min.
4. preparation method according to claim 2, which is characterized in that in step (1), the dosage and nothing of the deionized water
The dosage volume ratio of water alcohol is 5~50: 300；The time for continuing stirring is 5~20min；Time of the absolute ethyl alcohol washing
Number is 3~5 times.
5. preparation method according to claim 2, which is characterized in that in step (2), the chromium nitrate solution it is a concentration of
0.01~0.03mol/L；A concentration of 0.005~0.015mol/L of the ammonium tungstate solution；The concentration of the antimony chloride solution
For 0.01~0.02mol/L；A concentration of 0.05~0.15mol/L of the glacial acetic acid solution；The chromium nitrate solution, ammonium tungstate
The volume ratio of solution, antimony chloride solution and glacial acetic acid solution is 1: 0.5~1: 0.5~0.75: 0.5~0.75.
6. preparation method according to claim 2, which is characterized in that in step (3), the butyl titanate and absolute ethyl alcohol
Or the amount ratio of anhydrous propyl alcohol is 0.05~0.15: 200mol/mL；The time stirred and evenly mixed is 5~10min；The titanium
The molar ratio of acid butyl ester and citric acid is 0.05~0.15: 0.05~0.25；It is described continue the time stirred and evenly mixed for 10~
20min。
7. preparation method according to claim 2, which is characterized in that in step (3), the butyl titanate and polyvinyl
The mass ratio of pyrrolidones is 17~51: 0.5~1.5；After adding in polyvinylpyrrolidone, it is further continued for the time stirred and evenly mixed
For 10~30min.
8. preparation method according to claim 2, which is characterized in that in step (4), the mixing of the solution A and solution B
Volume ratio is 0.5: 1~5；Solution A is 1~1.5 hour with the time that solution B stirs and evenly mixs；The spherical titanium dioxide of monodisperse
The solid-liquid ratio of titanium particle and mixed solution is 50~100: 80~150g/mL.
9. preparation method according to claim 2, which is characterized in that in step (4), add in monodisperse spherical titanium dioxide
After particle, it is 0.5~5 hour to continue the time stirred and evenly mixed；The drying is 1~1.5 hour dry at 80~100 DEG C.
10. preparation method according to claim 2, which is characterized in that in step (4), the heat treatment be with 250~
After the heating rate of 300 DEG C/h is warming up to 700~1100 DEG C, heat preservation heat treatment 3~5 hours；The cooling is to be cooled to room temperature.
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